CA2875157A1 - Method for stabilizing polymers containing ester groups - Google Patents
Method for stabilizing polymers containing ester groups Download PDFInfo
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- CA2875157A1 CA2875157A1 CA2875157A CA2875157A CA2875157A1 CA 2875157 A1 CA2875157 A1 CA 2875157A1 CA 2875157 A CA2875157 A CA 2875157A CA 2875157 A CA2875157 A CA 2875157A CA 2875157 A1 CA2875157 A1 CA 2875157A1
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- liquid
- carbodiimides
- ester groups
- containing ester
- carbodiimide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Abstract
The invention relates to methods for stabilizing thermoplastic polyurethanes (TPU) containing ester groups, characterized in that carbodiimides of the formula (I) (see formula I) are added in liquid-dosed form in the course of preparation thereof and/or processing thereof.
Description
METHOD FOR STABILIZING POLYMERS CONTAINING ESTER GROUPS
The invention relates to methods for stabilizing polymers containing ester groups, in which monomeric aromatic carbodiimides are added in liquid-dosed form in the course of preparation and/or processing thereof.
Carbodiimides have been found to be useful in many applications, for example as hydrolysis stabilizers for thermoplastics, polyols, polyurethanes, etc.
Preference is given to using sterically hindered carbodiimides for this purpose. A carbodiimide that is particularly well known in this connection is 2,6-diisopropylphenylcarbodiimide (Stabaxol I from Rhein Chemie Rheinau GmbH).
The carbodiimides known in the prior art for this purpose, however, have the disadvantages of being volatile even at low temperatures. They are thermally unstable and exhibit a significant tendency to blocking in powder form. Used as a stabilizer in polymeric systems, they have the disadvantage that they are not free-flowing, and so first have to be melted prior to application and can only then be metered in.
There is therefore a need for sterically hindered carbodiimides which are usable for this purpose and which do not have the aforementioned disadvantages.
It was therefore an object of the present invention to provide a method for stabilizing polymers containing ester groups, wherein the stabilizers are thermally stable and storage-stable, are present as a mobile liquid even at room temperature, are easily preparable and can be applied in liquid form.
This object was surprisingly achieved by the use of particular monomeric carbodiimides.
The present invention therefore provides a method for stabilizing polymers containing ester groups, in which carbodiimides of the formula (I) RI
N=C=N (I) in which RI, R2, R4 and R6 is each independently C3-C6-alkyl
The invention relates to methods for stabilizing polymers containing ester groups, in which monomeric aromatic carbodiimides are added in liquid-dosed form in the course of preparation and/or processing thereof.
Carbodiimides have been found to be useful in many applications, for example as hydrolysis stabilizers for thermoplastics, polyols, polyurethanes, etc.
Preference is given to using sterically hindered carbodiimides for this purpose. A carbodiimide that is particularly well known in this connection is 2,6-diisopropylphenylcarbodiimide (Stabaxol I from Rhein Chemie Rheinau GmbH).
The carbodiimides known in the prior art for this purpose, however, have the disadvantages of being volatile even at low temperatures. They are thermally unstable and exhibit a significant tendency to blocking in powder form. Used as a stabilizer in polymeric systems, they have the disadvantage that they are not free-flowing, and so first have to be melted prior to application and can only then be metered in.
There is therefore a need for sterically hindered carbodiimides which are usable for this purpose and which do not have the aforementioned disadvantages.
It was therefore an object of the present invention to provide a method for stabilizing polymers containing ester groups, wherein the stabilizers are thermally stable and storage-stable, are present as a mobile liquid even at room temperature, are easily preparable and can be applied in liquid form.
This object was surprisingly achieved by the use of particular monomeric carbodiimides.
The present invention therefore provides a method for stabilizing polymers containing ester groups, in which carbodiimides of the formula (I) RI
N=C=N (I) in which RI, R2, R4 and R6 is each independently C3-C6-alkyl
- 2 -and R3 and R5 is each independently Ci-C3-alkyl, are added in liquid-dosed form in continuous or batchwise processes for preparation and/or processing thereof.
The C3-C6-alkyl radicals may be linear and/or branched. They are preferably branched.
In the carbodiimides of the formula (I) used in the process according to the invention, the RI to R6 radicals are preferably the same.
In a further preferred embodiment of the invention, the RI to R6 radicals are isopropyl.
The carbodiimides are liquid at room temperature and preferably have viscosities at 25 C of less than 2000 mPas, more preferably of less than 1000 mPas.
The scope of the invention includes all general radical definitions, indices, parameters and illustrations mentioned above and below, and those mentioned in preferred ranges with one another, i.e. also any combinations between the respective ranges and preferred ranges.
The compounds of the formula (I) are storage-stable and liquid at room temperature, and feature excellent meterability.
These carbodiimides are preparable by the carbodiimidization of trisubstituted benzene isocyanates of the formula (II) R4 cal R5 lir OD
N
and
The C3-C6-alkyl radicals may be linear and/or branched. They are preferably branched.
In the carbodiimides of the formula (I) used in the process according to the invention, the RI to R6 radicals are preferably the same.
In a further preferred embodiment of the invention, the RI to R6 radicals are isopropyl.
The carbodiimides are liquid at room temperature and preferably have viscosities at 25 C of less than 2000 mPas, more preferably of less than 1000 mPas.
The scope of the invention includes all general radical definitions, indices, parameters and illustrations mentioned above and below, and those mentioned in preferred ranges with one another, i.e. also any combinations between the respective ranges and preferred ranges.
The compounds of the formula (I) are storage-stable and liquid at room temperature, and feature excellent meterability.
These carbodiimides are preparable by the carbodiimidization of trisubstituted benzene isocyanates of the formula (II) R4 cal R5 lir OD
N
and
3 lei R1 R
0 (III) N%C
in which RI, R2, R4 and R6 is each independently C3-C6-alkyl and R3 and R5 is each independently C1-C3-alkyl, with elimination of carbon dioxide at temperatures of 40 C to 200 C in the presence of catalysts and optionally solvents.
The trisubstituted benzene isocyanates are preferably 2,4,6-triisopropylphenyl isocyanate, 2,6-diisopropy1-4-ethylphenyl isocyanate and 2,6-diisopropy1-4-methylphenyl isocyanate. The trisubstituted benzene amines needed for the preparation thereof can ¨ as is known to those skilled in the art ¨ be prepared by a Friedel-Crafts alkylation of aniline with the appropriate alkene, haloalkane, haloalkenebenzene and/or halocycloalkane.
Subsequently, they are reacted with phosgene to give the corresponding trisubstituted benzene isocyanate.
The carbodiimidization is preferably effected by the methods described in Angew. Chem. 93, p.
855 - 866 (1981) or DE-A-11 30 594 or Tetrahedron Letters 48 (2007), p. 6002 -6004.
Preferred catalysts for the preparation of the compounds of the formula (I), in one embodiment of the invention, are strong bases or phosphorus compounds. Preference is given to using phospholene oxides, phospholidines or phospholine oxides, and the corresponding sulfides. It is also possible to use, as catalysts, tertiary amines, basic metal compounds, alkali metal or alkaline earth metal oxides or hydroxides, alkoxides or phenoxides, metal carboxylates and non-basic organometallic compounds.
The carbodiimidization can be performed either in substance or in a solvent.
It is likewise possible first to commence the carbodiimidization in substance and subsequently to complete it after addition of a solvent. Solvents used may, for example, be benzines, benzene and/or alkylbenzenes.
Preferably, the carbodiimides for use in the process according to the invention are purified before they are used. The crude products can be purified either by distillation or by means of extraction.
Suitable solvents used for the purification may, for example, be alcohols, ketones, ethers or esters.
It is also likewise possible to prepare the carbodiimides for use in the process according to the invention from the trisubstituted anilines by reaction with CS2 to give the thiourea derivative and subsequent reaction in basic hypochlorite solutions to give the carbodiimide, or by the methods described in EP 0597382A.
The liquid dosage in the process according to the invention is effected batchwise or continuously, preferably in continuous processing machines, for example single-shaft, twin-shaft and multi-shaft extruders, continuous co-kneaders (Buss type) and/or batchwise kneaders, for example Banbury type, and other units customary in the polymer industry. This can be effected right at the start of or
0 (III) N%C
in which RI, R2, R4 and R6 is each independently C3-C6-alkyl and R3 and R5 is each independently C1-C3-alkyl, with elimination of carbon dioxide at temperatures of 40 C to 200 C in the presence of catalysts and optionally solvents.
The trisubstituted benzene isocyanates are preferably 2,4,6-triisopropylphenyl isocyanate, 2,6-diisopropy1-4-ethylphenyl isocyanate and 2,6-diisopropy1-4-methylphenyl isocyanate. The trisubstituted benzene amines needed for the preparation thereof can ¨ as is known to those skilled in the art ¨ be prepared by a Friedel-Crafts alkylation of aniline with the appropriate alkene, haloalkane, haloalkenebenzene and/or halocycloalkane.
Subsequently, they are reacted with phosgene to give the corresponding trisubstituted benzene isocyanate.
The carbodiimidization is preferably effected by the methods described in Angew. Chem. 93, p.
855 - 866 (1981) or DE-A-11 30 594 or Tetrahedron Letters 48 (2007), p. 6002 -6004.
Preferred catalysts for the preparation of the compounds of the formula (I), in one embodiment of the invention, are strong bases or phosphorus compounds. Preference is given to using phospholene oxides, phospholidines or phospholine oxides, and the corresponding sulfides. It is also possible to use, as catalysts, tertiary amines, basic metal compounds, alkali metal or alkaline earth metal oxides or hydroxides, alkoxides or phenoxides, metal carboxylates and non-basic organometallic compounds.
The carbodiimidization can be performed either in substance or in a solvent.
It is likewise possible first to commence the carbodiimidization in substance and subsequently to complete it after addition of a solvent. Solvents used may, for example, be benzines, benzene and/or alkylbenzenes.
Preferably, the carbodiimides for use in the process according to the invention are purified before they are used. The crude products can be purified either by distillation or by means of extraction.
Suitable solvents used for the purification may, for example, be alcohols, ketones, ethers or esters.
It is also likewise possible to prepare the carbodiimides for use in the process according to the invention from the trisubstituted anilines by reaction with CS2 to give the thiourea derivative and subsequent reaction in basic hypochlorite solutions to give the carbodiimide, or by the methods described in EP 0597382A.
The liquid dosage in the process according to the invention is effected batchwise or continuously, preferably in continuous processing machines, for example single-shaft, twin-shaft and multi-shaft extruders, continuous co-kneaders (Buss type) and/or batchwise kneaders, for example Banbury type, and other units customary in the polymer industry. This can be effected right at the start of or
- 4 -in the course of preparation of the polymer containing ester groups, or right at the start of or in the course of processing, for example to give monofilaments, or to give polymer pellets.
"Liquid-dosed" in the context of the invention is understood to mean that the aforementioned carbodiimides of the formula (I) are metered in liquid form, by gravimetric or volumetric means, into the continuous or batchwise processing machines. In order to enable this, the inventive carbodiimides must be liquid and of low viscosity on dosage thereof, especially at ambient temperature, as is customary in polymer processing. For liquid dosage in processing operations, the continuous dosage units customary in thermoplastic compounding technology are used. These may be heatable. They are preferably not heatable.
It is also likewise possible to use liquid mixtures of carbodiimides of the formula (I) in combination with other sterically demanding polymeric and/or monomeric carbodiimides, for example polymeric carbodiimide based on tetramethylxylylene diisocyanate and/or bis(2,6-diisopropylphenyl)carbodiimide.
The term "continuous process" in the context of the invention means that all the formulation constituents, including the liquid carbodiimide, have the proportion by mass prescribed in the formulation at any juncture in the metered addition and processing.
The term "batchwise process" in the context of the invention means that all the formulation constituents, including the liquid carbodiimide, have the proportion by mass prescribed in the formulation at the end of the metered addition.
The proportion by mass of the carbodiimide depends on the later use and is preferably 0.1 to 5%
by weight, more preferably 0.5 to 3% by weight, most preferably 1-2% by weight.
The liquid dosage of the carbodiimide is effected preferably at temperatures of 5 to 120 C, more preferably at 5 to 40 C, more preferably at 10 to 35 C.
The polymers containing ester groups are preferably thermoplastic polyurethanes (TPU).
These are commercial products which can be obtained, for example, from Bayer MaterialScience AG.
Examples for the preparation of polymers containing ester groups and processing thereof preferably include thermoplastic polyurethanes (TPU) and PU elastomers. The term "PU
elastomer" includes hot-cast and cold-cast elastomers based on polyurethane.
TPU, and also PU
elastomers, are prepared by polyaddition during processing. For this purpose, all the raw materials and additives in liquid and/or solid form are fed simultaneously to the compounding extruder in a
"Liquid-dosed" in the context of the invention is understood to mean that the aforementioned carbodiimides of the formula (I) are metered in liquid form, by gravimetric or volumetric means, into the continuous or batchwise processing machines. In order to enable this, the inventive carbodiimides must be liquid and of low viscosity on dosage thereof, especially at ambient temperature, as is customary in polymer processing. For liquid dosage in processing operations, the continuous dosage units customary in thermoplastic compounding technology are used. These may be heatable. They are preferably not heatable.
It is also likewise possible to use liquid mixtures of carbodiimides of the formula (I) in combination with other sterically demanding polymeric and/or monomeric carbodiimides, for example polymeric carbodiimide based on tetramethylxylylene diisocyanate and/or bis(2,6-diisopropylphenyl)carbodiimide.
The term "continuous process" in the context of the invention means that all the formulation constituents, including the liquid carbodiimide, have the proportion by mass prescribed in the formulation at any juncture in the metered addition and processing.
The term "batchwise process" in the context of the invention means that all the formulation constituents, including the liquid carbodiimide, have the proportion by mass prescribed in the formulation at the end of the metered addition.
The proportion by mass of the carbodiimide depends on the later use and is preferably 0.1 to 5%
by weight, more preferably 0.5 to 3% by weight, most preferably 1-2% by weight.
The liquid dosage of the carbodiimide is effected preferably at temperatures of 5 to 120 C, more preferably at 5 to 40 C, more preferably at 10 to 35 C.
The polymers containing ester groups are preferably thermoplastic polyurethanes (TPU).
These are commercial products which can be obtained, for example, from Bayer MaterialScience AG.
Examples for the preparation of polymers containing ester groups and processing thereof preferably include thermoplastic polyurethanes (TPU) and PU elastomers. The term "PU
elastomer" includes hot-cast and cold-cast elastomers based on polyurethane.
TPU, and also PU
elastomers, are prepared by polyaddition during processing. For this purpose, all the raw materials and additives in liquid and/or solid form are fed simultaneously to the compounding extruder in a
- 5 -continuous manner, or batchwise in a stirred reactor. In the compounding extruder, the mixing and polyaddition proceed to give the finished, polymeric, additized thermoplastic, TPU.
Preference is further given to TPU which is only stabilized on completion of polyaddition, by continuous metered addition of the liquid carbodiimides into the molten TPU in the compounding extruder by means of continuous metering units.
The examples which follow serve to illustrate the invention but have no limiting effect.
Preference is further given to TPU which is only stabilized on completion of polyaddition, by continuous metered addition of the liquid carbodiimides into the molten TPU in the compounding extruder by means of continuous metering units.
The examples which follow serve to illustrate the invention but have no limiting effect.
- 6 -Workin2 examples A liquid polymeric carbodiimide based on tetramethylxylylene diisocyanate available under the Stabaxol P 200 name and a monomeric carbodiimide (bis(2,6-diisopropylphenyl)carbodiimide), available under the Stabaxol I name from Rhein Chemie Rheinau GmbH, was tested in comparison with the inventive liquid monomeric carbodiimide (CDI I) of the formula N=C=N where the RI to R6 radicals are isopropyl, in polyester polyol of the Desmophen 2001 KS type from Bayer MaterialScience AG.
Preparation of the carbodiimide used in accordance with the invention A baked-out and nitrogen-filled 500 ml flange vessel was initially charged under a nitrogen stream with 400 g of 2,4,6-triisopropylphenyl isocyanate and heated to 140 C. After adding 400 mg of 1-methylphospholene oxide, the reaction mixture was heated to 160 C within 5 hours. Thereafter, reaction was continued at 160 C until an NCO content of <1% (corresponding to >95%
conversion) had been attained. The crude product thus obtained was purified by means of distillation. The product obtained was a pale yellow liquid having the viscosity of 700 mPas at 25 C.
Thermal stability To study the thermal stability, thermogravimetry analyses were conducted with a TGA analysis unit from Mettler Toledo (TGA851). For this purpose, 10-15 mg in each case of samples were analyzed under nitrogen with a temperature ramp from 30 to 600 C at a heating rate of 10 C/min.
The temperature in C on attainment of a weight loss of 5% was assessed [T(5%)].
Preparation of the carbodiimide used in accordance with the invention A baked-out and nitrogen-filled 500 ml flange vessel was initially charged under a nitrogen stream with 400 g of 2,4,6-triisopropylphenyl isocyanate and heated to 140 C. After adding 400 mg of 1-methylphospholene oxide, the reaction mixture was heated to 160 C within 5 hours. Thereafter, reaction was continued at 160 C until an NCO content of <1% (corresponding to >95%
conversion) had been attained. The crude product thus obtained was purified by means of distillation. The product obtained was a pale yellow liquid having the viscosity of 700 mPas at 25 C.
Thermal stability To study the thermal stability, thermogravimetry analyses were conducted with a TGA analysis unit from Mettler Toledo (TGA851). For this purpose, 10-15 mg in each case of samples were analyzed under nitrogen with a temperature ramp from 30 to 600 C at a heating rate of 10 C/min.
The temperature in C on attainment of a weight loss of 5% was assessed [T(5%)].
- 7 -The results are shown in Table 1:
Carbodiimide T(5%) of carbodiimide [ C]
Stabaxol I (C) 200 Stabaxol P 200 (C) 270 CDI I (inv.) 260 C = comparative example, inv. = inventive Acid number decrease in polyester polyol As is known, the effect of a hydrolysis stabilizer based on sterically hindered carbodiimides in liquid polyester polyols can be tested by means of acid degradation.
The decrease in acid number was tested using CDI I compared to the abovementioned StabaxoleI
and Stabaxol P 200 in the polyester polyol Desmophen 2001 KS from Bayer MaterialScience AG.
For this purpose, at 80 C, 1% by weight of the abovementioned carbodiimides was stirred into polyester polyol having a measured acid number of about 0.9 mg KOH/g and the acid number was measured regularly.
The results are shown in Table 2:
Acid Acid Acid Acid Acide Acid number number number number number number Carbodiimide in Desmophene 2001 [mg [mg [mg [mg [mg [mg KS
KOH/g] KOH/g] KOH/g] KOH/g] KOH/g] KOH/g]
after 0 after 30 after 60 after 120 after 240 after 480 min min min min min min CDI I (inv.) 0.86 0.51 0.27 0.09 0.00 Stabaxol I (C) 0.92 0.67 0.45 0.26 0.12 0.04 Stabaxol P 200 0.87 0.69 0.55 0.42 0.35 0.28 (C) C = comparative example, inv. = inventive The results in tables 1 and 2 show that the method according to the invention, with the use of liquid monomeric carbodiimides, as well as great advantages in terms of handling, also leads to a very rapid decrease in acid number with simultaneously very good thermal stability.
Carbodiimide T(5%) of carbodiimide [ C]
Stabaxol I (C) 200 Stabaxol P 200 (C) 270 CDI I (inv.) 260 C = comparative example, inv. = inventive Acid number decrease in polyester polyol As is known, the effect of a hydrolysis stabilizer based on sterically hindered carbodiimides in liquid polyester polyols can be tested by means of acid degradation.
The decrease in acid number was tested using CDI I compared to the abovementioned StabaxoleI
and Stabaxol P 200 in the polyester polyol Desmophen 2001 KS from Bayer MaterialScience AG.
For this purpose, at 80 C, 1% by weight of the abovementioned carbodiimides was stirred into polyester polyol having a measured acid number of about 0.9 mg KOH/g and the acid number was measured regularly.
The results are shown in Table 2:
Acid Acid Acid Acid Acide Acid number number number number number number Carbodiimide in Desmophene 2001 [mg [mg [mg [mg [mg [mg KS
KOH/g] KOH/g] KOH/g] KOH/g] KOH/g] KOH/g]
after 0 after 30 after 60 after 120 after 240 after 480 min min min min min min CDI I (inv.) 0.86 0.51 0.27 0.09 0.00 Stabaxol I (C) 0.92 0.67 0.45 0.26 0.12 0.04 Stabaxol P 200 0.87 0.69 0.55 0.42 0.35 0.28 (C) C = comparative example, inv. = inventive The results in tables 1 and 2 show that the method according to the invention, with the use of liquid monomeric carbodiimides, as well as great advantages in terms of handling, also leads to a very rapid decrease in acid number with simultaneously very good thermal stability.
Claims (5)
1. A method for stabilizing polymers containing ester groups, characterized in that carbodiimides of the formula (I) where R1, R2, R4 and R6 is each independently C3-C6-alkyl and R3 and R5 is each independently C1-C3-alkyl, are added in liquid form (liquid-dosed) in continuous or batchwise processes for preparation and/or processing thereof.
2. The method as claimed in claim 1, characterized in that the R1 to R6 radicals are the same within the molecule.
3. The method as claimed in claim 1 or 2, characterized in that the R1 to R6 radicals are isopropyl.
4. The method as claimed in one or more of claims 1 to 3, characterized in that the liquid carbodiimide is added at temperatures of 10-35°C.
5. The method as claimed in one or more of claims 1 to 4, characterized in that the polymers are thermoplastic polyurethanes (TPU).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12170771.5 | 2012-06-05 | ||
| EP12170771.5A EP2671912B1 (en) | 2012-06-05 | 2012-06-05 | Method for stabilising polymers containing ester groups |
| PCT/EP2013/056158 WO2013182330A1 (en) | 2012-06-05 | 2013-03-22 | Method for stabilizing polymers containing ester groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2875157A1 true CA2875157A1 (en) | 2013-12-12 |
| CA2875157C CA2875157C (en) | 2020-07-14 |
Family
ID=47915278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2875157A Active CA2875157C (en) | 2012-06-05 | 2013-03-22 | Method for stabilizing polymers containing ester groups |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20150175776A1 (en) |
| EP (1) | EP2671912B1 (en) |
| JP (1) | JP6174688B2 (en) |
| KR (1) | KR102019532B1 (en) |
| CN (1) | CN104364306A (en) |
| BR (1) | BR112014030444B1 (en) |
| CA (1) | CA2875157C (en) |
| DK (1) | DK2671912T3 (en) |
| ES (1) | ES2541410T3 (en) |
| HU (1) | HUE026635T2 (en) |
| IN (1) | IN2014DN10258A (en) |
| MX (1) | MX2014014974A (en) |
| PL (1) | PL2671912T3 (en) |
| PT (1) | PT2671912E (en) |
| RU (1) | RU2624299C2 (en) |
| WO (1) | WO2013182330A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LT6658B (en) * | 2017-12-08 | 2019-09-25 | Douglas Craig | Pet processing method |
| CN108912014A (en) * | 2018-06-22 | 2018-11-30 | 上海朗亿功能材料有限公司 | A kind of liquid-type carbodiimide compound preparation method and application |
| EP3686239A1 (en) | 2019-01-23 | 2020-07-29 | LANXESS Deutschland GmbH | Hydrolytically stabilised polyethylene terephthalate (pet) - containing compositions |
| EP4361209A1 (en) * | 2022-10-27 | 2024-05-01 | LANXESS Deutschland GmbH | Hydrolytically stabilised polyester compositions |
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|---|---|---|---|---|
| DE1130594B (en) | 1956-07-30 | 1962-05-30 | Du Pont | Process for the production of possibly modified polycondensation products with N? C? N bridge members |
| NL130563C (en) * | 1960-12-31 | |||
| US3798198A (en) * | 1969-12-19 | 1974-03-19 | Shoe & Allied Trades Res Ass | Hydrolytically stabilized polyurethanes |
| US3711439A (en) * | 1970-11-27 | 1973-01-16 | Inmont Corp | Stabilized polyurethane compositions |
| DE3930845A1 (en) * | 1989-09-15 | 1991-03-28 | Hoechst Ag | POLYESTER FIBERS MODIFIED WITH CARBODIIMIDES AND METHOD FOR THEIR PRODUCTION |
| DE4238046A1 (en) * | 1992-11-11 | 1994-05-19 | Basf Ag | New bis (4-substituted-2,6-diisopropylphenyl) carbodiimides, a process for their preparation and their use and the 4-substituted 2,6-diisopropylphenyl isocyanates which can be used for their preparation |
| US6013340A (en) * | 1995-06-07 | 2000-01-11 | Nike, Inc. | Membranes of polyurethane based materials including polyester polyols |
| DE19920276A1 (en) * | 1999-05-04 | 2000-11-09 | Basf Ag | Thermoplastic molding compounds |
| DE10161863A1 (en) | 2001-12-14 | 2003-07-03 | Basf Ag | Stabilizer composition II |
| JP3894846B2 (en) * | 2002-06-19 | 2007-03-22 | 平岡織染株式会社 | Flame retardant mesh sheet |
| KR20050004379A (en) * | 2003-07-02 | 2005-01-12 | 삼성전자주식회사 | Gas supplying apparatus for atomic layer deposition |
| US8247156B2 (en) * | 2010-09-09 | 2012-08-21 | Xerox Corporation | Processes for producing polyester latexes with improved hydrolytic stability |
| CN102816087A (en) * | 2011-06-10 | 2012-12-12 | 上海朗亿功能材料有限公司 | Method for preparing hydrolysis stabilizer for adhesive |
-
2012
- 2012-06-05 HU HUE12170771A patent/HUE026635T2/en unknown
- 2012-06-05 PT PT121707715T patent/PT2671912E/en unknown
- 2012-06-05 EP EP12170771.5A patent/EP2671912B1/en active Active
- 2012-06-05 PL PL12170771T patent/PL2671912T3/en unknown
- 2012-06-05 ES ES12170771.5T patent/ES2541410T3/en active Active
- 2012-06-05 DK DK12170771.5T patent/DK2671912T3/en active
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2013
- 2013-03-22 RU RU2014153978A patent/RU2624299C2/en active
- 2013-03-22 US US14/405,573 patent/US20150175776A1/en not_active Abandoned
- 2013-03-22 CN CN201380029611.2A patent/CN104364306A/en active Pending
- 2013-03-22 IN IN10258DEN2014 patent/IN2014DN10258A/en unknown
- 2013-03-22 BR BR112014030444-0A patent/BR112014030444B1/en active IP Right Grant
- 2013-03-22 CA CA2875157A patent/CA2875157C/en active Active
- 2013-03-22 WO PCT/EP2013/056158 patent/WO2013182330A1/en active Application Filing
- 2013-03-22 JP JP2015515427A patent/JP6174688B2/en active Active
- 2013-03-22 MX MX2014014974A patent/MX2014014974A/en active IP Right Grant
- 2013-03-22 KR KR1020147036864A patent/KR102019532B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| PT2671912E (en) | 2015-08-21 |
| PL2671912T3 (en) | 2015-10-30 |
| JP6174688B2 (en) | 2017-08-02 |
| BR112014030444B1 (en) | 2021-02-17 |
| RU2624299C2 (en) | 2017-07-03 |
| RU2014153978A (en) | 2016-07-27 |
| EP2671912A1 (en) | 2013-12-11 |
| ES2541410T3 (en) | 2015-07-20 |
| KR20150024868A (en) | 2015-03-09 |
| BR112014030444A2 (en) | 2017-06-27 |
| CA2875157C (en) | 2020-07-14 |
| CN104364306A (en) | 2015-02-18 |
| KR102019532B1 (en) | 2019-09-06 |
| HUE026635T2 (en) | 2016-07-28 |
| MX2014014974A (en) | 2015-03-13 |
| WO2013182330A1 (en) | 2013-12-12 |
| US20150175776A1 (en) | 2015-06-25 |
| EP2671912B1 (en) | 2015-04-22 |
| JP2015518911A (en) | 2015-07-06 |
| DK2671912T3 (en) | 2015-07-27 |
| IN2014DN10258A (en) | 2015-08-07 |
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